Fluorination is widely used in organic synthesis. As a kind of fluorinating reagent, triethylamine tris(hydrofluoride) has the advantage on top of others. Several applications of triethylamine tris(hydrofluoride) to organic synthesis are summarized according to reaction type, especially for nucleophilic substitution, the ring-opening fluorination reaction of epoxide, electrophilic addition, desilylation reaction and so on.